Dyes containing a vinyl sulfone



Patented Oct. 27,1953

DYES CONTAINING A VINYL SULFONE Johannes Heyna, Frankfurt am Main Unterliederbach, and Wilhelm Schumacher, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius und Bruning, Frankfurt am Main Hochst, Germany, a German company No Drawing. Application December 20, 1950, Serial N 0. 201,859. In Germany January 9, 1950 8 Claims.

The present invention relates to a process for producing fast dyeings and to the manufacture of dyestuffs for use therein. It is based on the observation that dyeings or prints of very good fastness properties can be produced on fibrous materials, and especially on nitrogenous fibrous materials, by applying to the material an acid dyestuff containing one or more groupings of the formula in which R represents hydrogen, a hydrocarbon radical of low molecular weight or halogen.

Acid dyestuffs, which contain one or more of the groupings SOz-CR CH2, may belong to various classes of dyestuffs. They may, for instance, be derived from the series of azo-dyestuffs, nitrodyestufis, anthraquinone-dyestuffs, 'tripheny1- methane-dyestuffs or the like.

The invention also relates to a process for the manufacture of dyestuffs which comprises introducing into the molecule of an acid dyestuff or a primary product thereof according to a known method one or more groupings of the formula in which R represents hydrogen, a hydrocarbon radical of low molecular weight or halogen.

The products may be prepared by various methods, for instance, by converting an acid dyestuff or a primary product into the sulfinic acid or the sodium salt of such acid, and then reacting the product with beta-chlorethyl alcohol or ethylene oxide or a homologue thereof. From the betahydroxy-ethyl-sulfones obtained by such a reaction, the compounds containing the group may be obtained in the usual manner, and these compounds, if primary products are concerned, may be condensed with reactive components Whih,'if required, may contain an acid group. Compounds of the present kind may also be prepared by subjecting to oxidation a compound containing the grouping -SCR=CH2 or the grouping SOCR=CH2. Finally neutral dyestuffs containing a vinylsulfone group may be sulfonated.

In the case of azo-dyestufis the grouping --SOz-CR=CHz may be present once or several times in the diazo-component or in the coupling component, or in both components. In the series of the azo-dyestufis the following examples may be mentioned as showing the types coming into consideration for the present process. The azodyestuffs from diazotized:

(1) 1-aminopheny1-3-viny1sulfone and 1-(2'- ,ohloro-'-sulfophenyl) 3 ,methyl-fi-pirrzohne,

(,2) I-amino-Z-methoxyphenyl 5 vinylsulfone and 1-hydroxynaphthalene-5-sulfonic acid,

(3) 1 aminophenyl-3-(alpha-bromovinyl)-sulfone and l-hydroxynaphthalene 5 sulfonic acid,

(4) 1-amino-2-methylphenyl-5-viny1sulfone and 1-hydroxynaphtha1ene-4-sulfonic acid,

(5) 1-amino-2-methylpheny1-5-vinylsulfone and 2 7 phenylamino-8-hydroxynaphthalene-6-su1- fonic acid,

(6) 1 aminonaphthyl 5 vinylsulfone and N- ethyl-N- (3-sulfobenzyl) -aniline,

(7 1 aminonaphthyl 5 vinylsulfone and N- ethyl-N- (3'-su1fobenzyl) -3-methyl-aniline,

(8) l-aminophenyl-4-vinylsulfone and l-amino- 8-hydroxynaphthalene-3 fi-disulfonic acid,

(9) 1-amino-2-methoxyphenyl 5 vinylsulfone and Z-amino-B-hydroxy naphthalene-G-sulfonic acid,

(10) 1 aminophenyl-3-sulfonic acid. and l-hydroxynaphthyl-4-vinylsulfone,

(11) 1-aminobenzene-4-sulfonic acid and l-hydroxy-naphthyl-5-vinylsulfone,

(12) l amino-2-methoxypheny1-5-vinylsulfone and 1-(6-chloro-2'-methy1-4'-su1fophenyl) -3- methyl-5-pyrazolone,

(13) 1 aminophenyl-3-(alpha-bromovinyl-sulfone) and l-hydroxynaphthalene 4 sulfonic acid,

(14) I-amino-Z-hydroxyphenyl 5 vinylsulfone and 2-aminonaphthalene-5-sulfonic acid with subsequent chroming,

(15) l-aminobenzene-B-sulfonic acid and 1-(3- vinylsulfonylphenyl) -3-methyl-3-pyrazolone,

( 16) 4-amino-2-methyl-4'-vinylsulfone-1:1'-azo benzene and Z-aminonaphthalene 6 sulfonic acid,

(17) 4-amino-2-sulfodiphenylamine and 1-aminonaphthyl-6-viny1sulfone, further diazotized and coupled with 2-hydroxy-naphthalene-6- sulfonic acid.

As further examples of dyestufis from other classes coming into consideration for the present process, the following dyestuifs may be named: (1) 2:4 dinitro 3-sulfo-4'-(2"-methoxy-5- vinylsulfonyl)-pheny1amino-diphenylamine of the formula (from 2:4-dinitro-l-chlorobenzene and -amino- 2 sulfo 2'-methoxydiphenylamino-5'-vinylsulfone).

OOH;

(2) 1-amino-2-sulfo-4-(2'-methoxy-5'-vinylsul- 3 fonyl) -phenylamino-anthraquinone of the formula N Hz,

SOsH

(from 1-aminoi-bromo-anthraquinone 12 sulfonic acid and l-amino-2-methoXyphenyl-5- vinylsulfone) (3) copper-phthalocyan divin-ylsulfone disulfonic acid from phthalic anhydride and phthalic anhydride vinyl sulfone with a subsequent sulfonation,

(4') l-amino-i 2 -.su1fo 4 (3' vinylsulfonyl') phenylaminoanthraquinone,

(5) the tertiary condensation productof cyanuric chloride with 1 mol of the monoazo-dyestufi obtained from diazotized l-aminophenyl tvinylsulfonew and l amino 2 methoxy 5"- methylbenzene, 1 mol of. the reduced monoa zo dyestufl, obtained from diazotized para-nitraniline and salicylic acid and 1 mole of; 1- aminobenzene-3-sulfonic acid.

(6) disulfonic acid of, the 1- :4di-(-3-'-vinylsulfonyl) phenyl-amino-anthraquinone from 1:4- dibromoanthraquinone and l-aminobenzene- 3-vinylsulfone with subsequent sulfonation,

(7) 2 :4-dinitro-6-sulfo 9 (3' vinylsulfonyl) phenyl-di-hydro phenazine of the formula (9) the condensation product of 1 mol of benzaldehyde-4-viny1sulfone and 2. molsof N- ethyl N-(3 sulfobenz Draniline of; the formula HOa 03-10 3.1GHz- The dyestuffs have a special afflnity for wool,

polyamide fibers; according to the structure of the basic dyestufi molecule, they may also be used with advantage for dyeing cotton, staple fibers or other fibrous materials of vegetable origin. The dyeings are produced in the usual manner, using, for instance, 1-3 per cent. of the dyestufi; calculated upon the fibrous material. The vinylsulfone dyestuff may also be produced in the dyebath before the dyeing. By means of the usual printing methods local dyeings may be produced. Owing. to the very reactive vinylsulfone group the dyestufis may enter into reaction with the reactiongroups of the fibrous material. Theymay alsov be polymerized on the fiber or they may be further condensed by reaction with compounds which are capable of reacting with vinylsulfone groups. By this procedure dyeings and prints are obtained which are distinguished byexcellent fastness properties.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight:

2 per cent. of the dyestuff of the formula OgNa dyes wool in-the usual manner from an acidbath. A vivid red dyeing of a good fastness to washing and to fulling in an alkaline solution, and a very good fastness to fulling. in an acid solution, to perspiration and sea-water is obtained. The remaining fastness properties, such. as fastness to rubbing, decatizing and: bleaching are very good.

Th dyestuff may be prepared as follows:

6.4 parts of 1amino-2-methoxyphenyl-5- vinylsulfone are diazotized in the usual manner and the diazo solution is-mixed at a temperature between 0 and 10- (3., in. the presence of sodium acetate with an aqueous solution of 16.6 parts of sodium l-hydroxy-naphthalene-iirsulionate (of 44.6: percent. strength). As soon as the coupling is complete, the dyestufi is filtered with suction, washed with: sodium chloride solution and dried.

A dyestuff with similar propertiesis obtained by using: 10.1 parts of sodium l-hydroxynaphthalene-4-sulfonate (oi, '73 per cent. strength) instead of sodium l-hydroxy-naphthalene-5-sulfonate.

E ample 2 2- per cent. ofthe-dyestufi ofthe formula dyes wool from a bath containing sulfuric acid or acetic acid. A fine, covered brown dyeing of good to very good fastness to washing and of good fastness to sea s-water and light isobtained. The decatizing, carbonizing' and stoving tests are likewise very good. The dyes-turf also has a good afiinity for unloaded silk and polyamide fibers.

It, maybe prepared as. tollows Amaze-solution p pa ed; the; usu l mann from 6.4 parts of 1-amino-2-methoxyphenyl-5- vinylsulfone is mixed at a temperature between C. and C. in the presence of sodium carbonate with an aqueous solution of 11.2 parts of 2-phenylamino-8-hydroxy-naphtha1ene 6 sulfonic acid of 85 per cent. strength. As soon as the coupling is complete, the dyestuff is worked up as described in Example 1.

Example 3 2.5 per cent. of the dyestufi of the formula NaOaS yields on wool a vivid yellow dyeing of a good fastness to fulling in an acid solution and to rubbing and a very good fastness to sea-water. The decatizing, carbonizing and stoving tests are likewise very good. The dyestufi also has a good afiinity for unloaded silk.

It may be prepared as follows:

A diazo solution prepared in the usual manner from 5.5 parts of 1-aminophenyl-3-vinylsulfone is run, in the presence of sodium acetate, while cooling with ice, into an aqueous solution of the sodium salt of 1-(2'-chloro-5'-sulfophenyl)-3- methyl-S-pyrazolone (of 83 per cent. strength). When the coupling is terminated, the dyestuff is completely precipitated by the addition of a concentrated solution of sodium chloride, then filtered with suction, washed with a concentrated sodium chloride solution and dried.

A dyestufi having similar properties is obtained by using the diazo compound of 7.86 parts of 1- aminophenyl 3 (alpha-bromo-vinylsulfone) of the formula instead of 1-aminophenyl-3-vinylsulfone.

Ewample 4 2 per cent. of the dyestufi of the formula NaOaB dyes wool from an acid bath. A vivid red dyeing of a very good fastness to washing, of a good fastness to sea-water and to rubbing and of a very good decatizing and carbonizing properties is obtained. The dyestuff also has a good affinity for unloaded silk.

It can be prepared as follows:

7 parts of l-aminonaphthy1-5-vinylsulfone are diazotized in the usual manner and the diazo W001 is dyed in the usual manner with 3 per cent. of the dyestuff of the formula SC NE The dyestulf dyes wool in bluish-black tints of a very good fastness to water, a good fastness to washing and a good to very good fastness to light.

It may be prepared as follows:

21 parts of 1-aminophenyl-4-vinylsulfone are diazotized in the usual manner. To the ice-cold, clear solution obtained, a solution of 34.1 parts of l-amino 8 hydroxy-naphthalene 3:6 disulfonic acid in 100 parts by volume of water and 5.5 parts of sodium carbonate is added, drop by drop, within 1 hour, while stirring well. Stirring is continued for 12 hours, the whole is heated to 50 C. and 20 parts of sodium hydroxide solution (of 30 per cent. strength) are added. This solution is mixed at 0 to 5 C. with a diazo solution of 9.3 parts of aniline. As soon as the coupling is complete, the whole is heated to C. and salted out with 5 per cent. of sodium chloride. The dyestuif is then filtered with suction, washed with a sodium chloride solution and dried.

If wool is dyed with 3 per cent. of the dyestufi of the formula NaOzS- OH NH: OCH;

similar results are obtained.

Example 6 4 parts of the dyestufi' of the formula are made up with water, thiodiglycol and a tragacanth thickening so as to form parts of a printing paste. After printing on wool, the wool is steamed for 20 minutes. A blue print of good fastness to washing and light is obtained. 7

When the dyestuff is dyed on wool in the usual manner from an acid bath, a clear, blue dyeing of a very good evenness and a good fastness, to washing and fulling is obtained. The dyestufl also has a good afiinity for unloaded silk.

- 7 it'ican be prepared-as follows .1 0.5 parts of -the compound' of the formula ACT-C 112-43 H:OH

(prepared bycondensing sodium 1 amino 4- bromoanthraquindne-Zsulfonate with l-amino- 2-methoxyphenyl 5 beta-hydroxyethylsulfone) are introduced at room .temperature while stirring, into 75 parts of sulfuric acid of 92 per cent. strength, and the whole is stirred for some hours -atroem temperature. The'sulfuric acid solution 'is'then poured 0nto"300-400-parts -0f ice.

sulfuric acid ester'which has separated is Well The filtered with suction and dissolved at 50-60 C. in 1500 to 2000 parts-of Water. The-blue solution obtained ismixed; Whilestirring, With dilute sodium hydroxidesolution unti1"the-reaction re- "mains alkaline. The 'd'yestu'ff -fOrmed-which cor- '-responds to-the'first formulagiven in this example 'is completely precipitated, While applying heatywith a'saturatedsodium chloride solution. After cooling, the dyestuff is filtered with suction,

washed-with dilutesodium chloride solution until 'neutraland dried.

The dyestufis of -the following formulae *NHa ' C O 0 --S 0311 o o r o.

0 0 (I -soau uuor-cn=cua which may be prepared in the same manner dye wool clear, blue tints of gooddastnessproperties.

and

Example 7 2 per cent. of thedyestufi of the formula dyes cotton from-aneutral bath. A bl'ue' tint of agood fastnessto' wet processinggand in particular ofa-good fastne'ss to water and washing-us obtained. 7

The dyestuff'is prep'ared by combiningthe tetrazo compound of 4.4 -'-diamino-3.j3-'dimethoxy-diphenyl first with 'z-hydroxy -naphthal'ene G-beta-hydroxy-eth'yl 'sulfone and then with 2- (2 nitro 4 beta hydroxy ethylsulfonyl) phenylamino 5 -'hydroXy-naphthalene '7 sulionic acid and transforming the dyestufi into the vinyl-sulfone compound=-according-=to the directions given above.

Exam-131a s Wool is dyed in'the uSu aImanner with 6 per cent. of the dyestufi of the formula 0 CH3 OH NH:

Sz-CEBCH: 503K 501B O2CH=CH2 mula are then introduced. After the coupling in an acid solution is complete, the solution of the monoazo dyestufi formed, having the formula oFGHz-oHPo-som is cooled, while stirring, to -5 CL; then mixed Example 9 with the diazo solution prepared in the usual 30 parts of the potassium Salt of the dyestufi manner with 4.3 parts of 2-amino I-methoxy t f jrfli ja',

phenyl-4-vinylsulfone, and rendered alkaline with 2N-sodium carbonate solution. When the cou- 5 9 pling is complete, the dyestufi solution can be rendered acid with hydrochloric acid and the dye- L stuff can be salted out With 15 per cent. of potassium chloride. The dyestufi is filtered with suc- 10 O 1 tion and then Washed with a potassium chloride solution until it is neutral to Congo paper. For E the transformation of the sulfuric acid ester into the vinylsulfone group the disazo dyestuif is dissolved in water and the solution obtained is mixed, at 25 -30 C. with dilute sodium hydroxide my c 01, 50 parts of triethanolamme n 200 parts Solutlon untll the reactlon remams feebly alka" of Water. The solution obtained is stirred with line. The divinylsulfone dyestuff formed iS then 400 parts of neutral tragacanth thickening and salted out with sodium chloride, filtered with made up to 1000 parts of printing paste. After suction and washed with sodium chloride solupi t s g f e 1 131011 and drbylnlg, thedngtena 15 s eame or our in a 0] er an en non 1131s neutral f f thoroughly rinsed in the cold. A vivid yellow In slmllar manner dlvmylsul one dyestuffs tint of good fastness to wet processing is obtained. of the following constitution may be prepared. 25 Exam le 10 These dyestuffs dye wool likewise in bluish-black 6 t d p d 1. th 0 fastness to wet rocessin A per yemg Pro uced on W00 W1 tints of Slmflar go d p g the dyestuff of the following formula OCHs OH NH: OH NH OH: I

0: H035 E OrCH-CH: Oz HOQS 0 H OrCHrCHrO-SOaH (5H 5 (EH t 1% 7 0H NH, CHz=CHOzSN=-N N=N G-BOZOH=CHI OH m GE1=CH-O2SON=N N=N Hogs sou: o=-cn=cm OH NH: 7 CH2=CHO2SON=N N=NQ 1103s 80,11 o=-on=cn,

OCH; 0H NH: which may be prepared as described in Example liquor and While adding 6 per cent. of secondary are dissolved with 10 parts of thiodiethylene I 8, is carried out as follows: The dyestufl? isdissolvedin water at 80 C., O Hogs 'SOaH OrCECH while maintainingthe usual ratio of goods to i sodium phosphate. The temperature of 80 0. HI V is maintained for about 15 minutes. Thedyebath is then rendered feebly acid by means of acetic OCHa OH NH:

the same good to very good fastness to wet proc- 75 essing:

acid and dyeing is carried out in the usual man- NWGSOTCECHQ ner. A bluish-black dyeing of good to very good N- fastness to wet processing is obtained. 0, H033 03H The followingdyestuffs yield dyeings exhibiting zssazieegi n 9 4 my.

0, mm CH PIE:

NO. OgNB Vivid red.

Vivid, bluish reg.

Yellow.

Clear orange.

Yellowish red.

Constitution Tint on wool (10) (I) O H; Yellow; aiterchromed: yellowish brown.

502CH=CH2 K (11) Cl Yellow; aiterchromed: yellowish brown.

A Or-CH=C H: O 0 K (12) Yellow; after-chromed: yellowish brown.

CHz=CHO:S N=NQOH (13) 0H 0H Bordeaux; alter-chromed: violet.

0 C H=C H,

S OaNa We claim: ness to wet processing and good to very good 1. Dyestuffs, selected from the class consisting of azo-dyestufis, nitro-dyestufis, anthraquinonedyestufis and triphenyl-methane-dyestuffs, oon

fastness to light.

6. The dyestufi corresponding to the following formula:

0H NH:

taining at least one sulfonic acid group and the grouping (--SOz-CR=CHz) n wherein R stands for a member of the group consisting of hydrogen, alkyl and bromine and 1:. stands for one of the numbers 1 and 2.

2. Azo-dyestuffs containing at least one sulfonic acid group and the grouping (--SO2CH=CH2) 11.

wherein n stands for one of the numbers 1 and 2.

3. Azo-dyestufis containing at least one sulfonic acid group and the grouping -SO2-CH=CH2 4. The dyestufl corresponding to the following formula:

OCH:

dyeing wool clear blue shades of a very good evenness and good fastness to washing, to fulling and to light.

5. The dyestufi corresponding the following formula 0 0 g soul dyeing wool clear blue shades of very good fast- SOr-CH=CHI dyeing wool bluish-black shades of very good fastness to wet processing, and good to very good fastness to light.

7. The dyestuff corresponding to the following formula:

CHFOH-OaSGNHQNH-O OaNa N02 dyeing wool medium brown shades of very good fastness to wet processing, and good to very good fastness to light.

8. The dyestufl corresponding to the following formula I NH: SOs-C H=O Ha dyeing wool vivid bluish-red shades of very good fastness to wet processing and good to very good fastness to light.

JOHANNES HEYNA. WILHELM SCHUMACHER. 

1. DYESTUFFS SELECTED FROM THE CLASS CONSISTING OF AZO-DYESTUFFS, NITRO-DYESTUFFS, ANTHRAQUINONEDYESTUFFS AND TRIPHENYL-METHANE-DYESTIFFS, CONTAINING AT LEAST ONE SULFONIC ACID GROUP AND THE GROUPING 